CN110120503A - A kind of composite positive pole and its preparation method and application - Google Patents
A kind of composite positive pole and its preparation method and application Download PDFInfo
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- CN110120503A CN110120503A CN201810111692.5A CN201810111692A CN110120503A CN 110120503 A CN110120503 A CN 110120503A CN 201810111692 A CN201810111692 A CN 201810111692A CN 110120503 A CN110120503 A CN 110120503A
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- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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Abstract
The invention discloses a kind of composite positive poles and its preparation method and application.Composite positive pole the preparation method comprises the following steps: by atomic molar ratio Li:Ni:Mn:B=(1-1.1): lithium source, nickel source, manganese source, boron source 0.5:1.5:(0.001-0.02), with water mix；Mist projection granulating obtains presoma powder body material；Pre-burning；High-temperature calcination again obtains the spherical nickel-lithium manganate of boron oxide compound cladding；It is dispersed in red phosphorus in the mixed solution of NMP and DMF, is heat-treated through ultrasound, mist projection granulating, 450-550 DEG C, 1.5-4.5h；The molar ratio of red phosphorus additional amount and lithium source additional amount is 0.01:(1-1.1).Composite positive pole of the invention can improve the chemical property of nickel ion doped, 500 circulation volume conservation rate highests of room temperature can be improved to 92.7%, gram volume highest that 0.5C is discharged for the first time is improved to 137.2mAh/g.
Description
Technical field
The present invention relates to the electrode material manufacturing fields of lithium ion battery, and in particular to a kind of composite positive pole and its system
Preparation Method and application.
Background technique
Chinese patent application CN104169221A discloses a kind of side of the manganese oxide of lithiumation for preparing nucleocapsid structure
Method is specifically the manganese oxide that lithiumation is coated using phosphorus pentoxide vapor deposition, since phosphorus pentoxide need to be used, this
Substance easy to absorb moisture causes additive amount to be difficult to control, thus influences the consistency of material.
Chinese patent application CN105914366A discloses a kind of spinel lithium-rich LiMn2O4 of the oxide of Boron Coated
Preparation method is specifically to be coated using boron oxide compound to rich lithium LiMn2O4, the performance of Lai Tigao material.But it is right
The cladding that the material prepared carries out belongs to ex situ cladding, not significant to the promotion effect of material property.
Chinese patent application CN104828878A discloses a kind of preparation method of the nickel ion doped material of graphene coated,
Specifically, it is to add graphene in the nickel ion doped material precursor stage, forms graphene coated in situ.But in nickel manganese
The sour lithium material presoma stage adds graphene, can also be also while graphene can be reacted with oxygen in high-temperature sintering process
Former part Mn4+It is converted into Mn3+, to be reduced the effect of cladding, Mn by a large amount of consumption3+Generation so that material cycle performance
It is deteriorated.
Since nickel ion doped electrode material is just widely used in recent years, and compound coating is generally also limited by into
The factors such as this height, complex process are related to the compound coating technique of nickel ion doped electrode material so rarely having in practical study, greatly
More open source literatures pertain only to homogenous material cladding, its material property is not obviously improved after cladding.
Summary of the invention
Present invention seek to address that the technical issues of be to overcome electrode material existing in the prior art after cladding, electricity
Chemical property promotes inapparent problem, and provide a kind of composite positive pole and its preparation method and application.The present invention mentions
A kind of composite positive pole and its preparation method and application has been supplied, the ball of phosphorous oxides Yu boron oxide compound compound coating can be obtained
Shape nickel ion doped improves the chemical property of nickel ion doped material.
The present invention provides a kind of (nickel ion doped of boron oxide compound and phosphorous oxides compound coating) composite positive pole,
In, the molecular formula of boron oxide compound is B2O3, the molecular formula of phosphorous oxides is P2O5。
The present invention provides a kind of preparation methods of composite positive pole comprising following steps:
(1) with atomic molar ratio Li:Ni:Mn:B=(1-1.1): 0.5:1.5:(0.001-0.02) take lithium source, nickel source, manganese
Source, boron source, are uniformly mixed to form solution with water；
(2) by acquired solution mist projection granulating, presoma powder body material is obtained；
(3) the presoma powder body material is subjected to pre-burning, obtains Preburning material；
(4) Preburning material is subjected to high-temperature calcination, obtains the spherical nickel-lithium manganate of boron oxide compound cladding；
(5) spherical nickel-lithium manganate of boron oxide compound cladding and red phosphorus are dispersed in the mixed solution of NMP and DMF,
Successively carry out ultrasound, mist projection granulating, heat treatment；The molar ratio of the additional amount of lithium source in the additional amount and raw material of the red phosphorus
For 0.01:(1-1.1)；The temperature of the heat treatment is 450-550 DEG C, time 1.5-4.5h.
In step (1), lithium source, nickel source, manganese source, boron source can be the raw material commonly used in the art in production electrode material, described
Lithium source is preferably one of lithium carbonate, lithium hydroxide, lithium acetate and lithium nitrate or a variety of；The nickel source is preferably oxalic acid
One of nickel, nickel oxide, nickel nitrate and nickel hydroxide are a variety of；The manganese source is preferably manganese acetate, manganese dioxide, four oxygen
Change one of three manganese and manganese nitrate or a variety of；The boron source is preferably boric acid and/or diboron trioxide.
In step (1), the atomic molar ratio preferably Li:Ni:Mn:B=1.005 of lithium source, nickel source, manganese source, boron source:
0.5:1.5:(0.005-0.02)。
In step (1), the water is deionized water commonly used in the art, and additional amount is that this field is conventional, preferably
For amount needed for the solid content of solution is adjusted to 15%-45%, more preferably for the solid content of solution is adjusted to needed for 20%
Amount, the percentage be mass percent.
In step (1), described be uniformly mixed is realized preferably by sanding operation.The equipment of the sand milling is that this field is normal
The sand milling device of rule, such as sand mill.The time of the sand milling keeps each material component in the solution mixed for this field routine
Time needed for until closing uniformly, preferably 0.5-5h is more preferably 1h.
Step (1)-(2) effect is, lithium source, nickel source, manganese source, boron source are uniformly mixed to form solution, done by spraying
After dry, spherical boron oxide compound in situ is made and coats nickel ion doped material precursor.
In step (3), the pre-burning carries out in the conventional equipment of this field, such as Muffle furnace.The technique item of the pre-burning
Part is this field normal condition, and temperature is preferably 350-550 DEG C, and the time is preferably 4-10h.
In step (4), the high-temperature calcination carries out in the conventional equipment of this field, such as tube furnace.The high-temperature calcination
Process conditions be this field normal condition, temperature is preferably 750-1000 DEG C, and the time is preferably 10-24h.
Cladding described in step (4) is in-stiu coating, and in-stiu coating is this field general term, is referred in materials synthesis
Covering material is added simultaneously, boron source is also joined while synthesizing nickel ion doped in step (1) in the application, plays and synthesized
Coating function in journey, is consequently belonging to in-stiu coating.In contrast, ex situ cladding refers to that materials synthesis adds again after complete
Covering material.
Step (3)-(4) effect is, is sintered using such as equipment such as Muffle furnace, tube furnace to presoma, closes
Nickel ion doped material is coated at spherical in-situ boron oxide.
In step (5), the mixed solution of the NMP and DMF are this field Conventional solvents, wherein the volume ratio of NMP and DMF
Preferably 2:1.The dosage of the mixed solution is to keep electrode material fully dispersed, the mixed solution and electrode material
Mass ratio be preferably 4:1.
In step (5), the condition of the ultrasound is this field normal condition, and the time of the ultrasound is preferably 0.5-
5h。
In step (5), the temperature of the heat treatment is preferably 500 DEG C, and the time is preferably 2h.
The present invention also provides the composite positive poles prepared by the preparation method.
The present invention also provides application of the above-mentioned composite positive pole in lithium ion battery.
On the basis of common knowledge of the art, above-mentioned each optimum condition, can any combination to get each preferable reality of the present invention
Example.
The reagents and materials used in the present invention are commercially available.
The positive effect of the present invention is that: composite positive pole provided by the invention can be improved nickel ion doped material
Chemical property, 500 circulation volume conservation rate highests of room temperature can be improved to 92.7%, 0.5C be discharged gram for the first time and to be held
Amount highest is improved to 137.2mAh/g.
Specific embodiment
The present invention is further illustrated below by the mode of embodiment, but does not therefore limit the present invention to the reality
It applies among a range.In the following examples, the experimental methods for specific conditions are not specified, according to conventional methods and conditions, or according to quotient
The selection of product specification.
In following embodiment and comparative examples, in the mixed solution of NMP used and DMF, the volume ratio of NMP and DMF are 2:
1；The dosage of mixed solution is 4 times of electrode material quality.
Embodiment 1
With molar ratio Li:Ni:Mn:B=1.005:0.5:1.5:0.005 weigh respectively lithium carbonate, nickel oxalate, manganese acetate,
Boric acid, suitable deionized water, which is added, makes its solid content 20%.1h is sanded to above-mentioned solution using sand mill, it is spray-dried
Powder body material is made afterwards.450 DEG C of pre-burning 7h of Muffle furnace, 900 DEG C of high-temperature calcination 12h of tube furnace are placed on, are obtained spherical former
Position boron oxide compound coats nickel lithium manganate cathode material.
It weighs spherical boron oxide compound cladding nickel ion doped in situ and red phosphorus is dispersed in the mixed solution of NMP and DMF,
After ultrasonic 1h is spray-dried, 500 DEG C of processing 2h of reaction kettle are placed it in, obtain sample 1；The additional amount and raw material of the red phosphorus
The molar ratio of the additional amount of middle lithium source is 0.01:1.005.After heat treatment, the preparation of 1 sample of embodiment is completed.
Embodiment 2
Lithium carbonate, nickel oxalate, manganese acetate, boron are weighed respectively with molar ratio Li:Ni:Mn:B=1.005:0.5:1.5:0.01
Acid, suitable deionized water, which is added, makes its solid content 20%.1h is sanded to above-mentioned solution using sand mill, after spray-dried
Powder body material is made.450 DEG C of pre-burning 7h of Muffle furnace, 900 DEG C of high-temperature calcination 12h of tube furnace are placed on, are obtained spherical in situ
Boron oxide compound coats nickel lithium manganate cathode material.
It weighs spherical boron oxide compound cladding nickel ion doped in situ and red phosphorus is dispersed in the mixed solution of NMP and DMF,
After ultrasonic 1h is spray-dried, 500 DEG C of processing 2h of reaction kettle are placed it in, obtain sample 2；The additional amount and raw material of the red phosphorus
The molar ratio of the additional amount of middle lithium source is 0.01:1.005.After heat treatment, the preparation of 2 sample of embodiment is completed.
Embodiment 3
With molar ratio Li:Ni:Mn:B=1.005:0.5:1.5:0.015 weigh respectively lithium carbonate, nickel oxalate, manganese acetate,
Boric acid, suitable deionized water, which is added, makes its solid content 20%.1h is sanded to above-mentioned solution using sand mill, it is spray-dried
Powder body material is made afterwards.450 DEG C of pre-burning 7h of Muffle furnace, 900 DEG C of high-temperature calcination 12h of tube furnace are placed on, are obtained spherical former
Position boron oxide compound coats nickel lithium manganate cathode material.
It weighs spherical boron oxide compound cladding nickel ion doped in situ and red phosphorus is dispersed in the mixed solution of NMP and DMF,
After ultrasonic 1h is spray-dried, 500 DEG C of processing 2h of reaction kettle are placed it in, obtain sample 3；The additional amount and raw material of the red phosphorus
The molar ratio of the additional amount of middle lithium source is 0.01:1.005.After heat treatment, the preparation of 3 sample of embodiment is completed.
Embodiment 4
Lithium carbonate, nickel oxalate, manganese acetate, boron are weighed respectively with molar ratio Li:Ni:Mn:B=1.005:0.5:1.5:0.02
Acid, suitable deionized water, which is added, makes its solid content 20%.1h is sanded to above-mentioned solution using sand mill, after spray-dried
Powder body material is made.450 DEG C of pre-burning 7h of Muffle furnace, 900 DEG C of high-temperature calcination 12h of tube furnace are placed on, are obtained spherical in situ
Boron oxide compound coats nickel lithium manganate cathode material.
It weighs spherical boron oxide compound cladding nickel ion doped in situ and red phosphorus is dispersed in the mixed solution of NMP and DMF,
After ultrasonic 1h is spray-dried, 500 DEG C of processing 2h of reaction kettle are placed it in, obtain sample 4；The additional amount and raw material of the red phosphorus
The molar ratio of the additional amount of middle lithium source is 0.01:1.005.After heat treatment, the preparation of 4 sample of embodiment is completed.
Embodiment 5
Lithium carbonate, nickel oxalate, manganese acetate, boric acid are weighed respectively with molar ratio Li:Ni:Mn:B=1:0.5:1.5:0.001,
Suitable deionized water, which is added, makes its solid content 20%.1h is sanded to above-mentioned solution using sand mill, is made after spray-dried
Obtain powder body material.450 DEG C of pre-burning 7h of Muffle furnace, 900 DEG C of high-temperature calcination 12h of tube furnace are placed on, spherical in-situ boron is obtained
Oxide coats nickel lithium manganate cathode material.
It weighs spherical boron oxide compound cladding nickel ion doped in situ and red phosphorus is dispersed in the mixed solution of NMP and DMF,
After ultrasonic 1h is spray-dried, 500 DEG C of processing 2h of reaction kettle are placed it in, obtain sample 5；The additional amount and raw material of the red phosphorus
The molar ratio of the additional amount of middle lithium source is 0.01:1.After heat treatment, the preparation of 5 sample of embodiment is completed.
Embodiment 6
Lithium carbonate, nickel oxalate, manganese acetate, boron are weighed respectively with molar ratio Li:Ni:Mn:B=1.1:0.5:1.5:0.001
Acid, suitable deionized water, which is added, makes its solid content 20%.1h is sanded to above-mentioned solution using sand mill, after spray-dried
Powder body material is made.450 DEG C of pre-burning 7h of Muffle furnace, 900 DEG C of high-temperature calcination 12h of tube furnace are placed on, are obtained spherical in situ
Boron oxide compound coats nickel lithium manganate cathode material.
It weighs spherical boron oxide compound cladding nickel ion doped in situ and red phosphorus is dispersed in the mixed solution of NMP and DMF,
After ultrasonic 1h is spray-dried, 500 DEG C of processing 2h of reaction kettle are placed it in, obtain sample 6；The additional amount and raw material of the red phosphorus
The molar ratio of the additional amount of middle lithium source is 0.01:1.1.After heat treatment, the preparation of 6 sample of embodiment is completed.
Embodiment 7
The temperature and time that final step is heat-treated in the present embodiment is respectively 450 DEG C of processing 4.5h, remaining raw material and work
Skill condition is the same as embodiment 2.
Embodiment 8
The temperature and time that final step is heat-treated in the present embodiment is respectively 550 DEG C of processing 1.5h, remaining raw material and work
Skill condition is the same as embodiment 2.
Comparative example 1
Lithium carbonate, nickel oxalate, manganese acetate are weighed respectively with molar ratio Li:Ni:Mn=1.005:0.5:1.5, are added appropriate
Deionized water make its solid content 20%.1h is sanded to above-mentioned solution using sand mill, obtained powder material after spray-dried
Material.450 DEG C of pre-burning 7h of Muffle furnace, 900 DEG C of high-temperature calcination 12h of tube furnace are placed on, spherical nickel-lithium manganate anode material is obtained
Material.
Comparative example 2
Lithium carbonate, nickel oxalate, manganese acetate, boron are weighed respectively with molar ratio Li:Ni:Mn:B=1.1:0.5:1.5:0.03
Acid, suitable deionized water, which is added, makes its solid content 20%.1h is sanded to above-mentioned solution using sand mill, after spray-dried
Powder body material is made.450 DEG C of pre-burning 7h of Muffle furnace, 900 DEG C of high-temperature calcination 12h of tube furnace are placed on, are obtained spherical in situ
Boron oxide compound coats nickel lithium manganate cathode material.
It weighs spherical boron oxide compound cladding nickel ion doped in situ and red phosphorus is dispersed in the mixed solution of NMP and DMF,
After ultrasonic 1h is spray-dried, 500 DEG C of processing 2h of reaction kettle are placed it in, obtain 2 sample of comparative example；The additional amount of the red phosphorus
Molar ratio with the additional amount of lithium source in raw material is 0.03:1.1.After heat treatment, the preparation of 2 sample of comparative example is completed.
Effect example 1
Battery performance characterization is carried out to composite positive pole made from embodiment 1-8, comparative example 1-2.
The specific test method is as follows: composite positive pole and conductive agent Super P, polyfluortetraethylene of binding element lotion are pressed
Mass ratio 80:10:10 is uniformly mixed in N-Methyl pyrrolidone, is coated onto aluminium foil surface using wet process coating device, and 80
It is dried in DEG C baking oven, to the electrode disk for being 10mm with slicer interception diameter after roller compaction, 80 DEG C are dried in vacuo 24 hours, choosing
It is diaphragm with Ceglard 2300, using metal lithium sheet as cathode, the ethylene carbonate and carbonic acid diformazan of 1mol/L lithium hexafluoro phosphate
The solution of ester is assembled into CR2016 type button cell in being full of argon gas glove box as electrolyte, after standing for 24 hours at room temperature,
Charge and discharge cycles test is carried out under 2001 equipment of LAND CT of Wuhan Jin Nuo Electronics Co., Ltd. production, the results are shown in Table 1.
It is good that chemical property can be obtained by the technical solution that the data of table 1 can be seen that the embodiment of the present application
The performance for the nickel ion doped that nickel ion doped material, especially embodiment 2 obtain is best, 500 circulation volumes of room temperature can be protected
Holdup improves to 92.7%, 0.5C the gram volume that discharges for the first time and improves to 137.2mAh/g.
1 CR2016 type Button cell tests data comparison of table
Claims (10)
1. a kind of preparation method of composite positive pole, which is characterized in that it includes the following steps:
(1) by atomic molar ratio Li:Ni:Mn:B=(1-1.1): 0.5:1.5:(0.001-0.02) lithium source, nickel source, manganese source,
Boron source is uniformly mixed to form solution with water；
(2) by acquired solution mist projection granulating, presoma powder body material is obtained；
(3) the presoma powder body material is subjected to pre-burning, obtains Preburning material；
(4) Preburning material is subjected to high-temperature calcination, obtains the spherical nickel-lithium manganate of boron oxide compound cladding；
(5) spherical nickel-lithium manganate of boron oxide compound cladding and red phosphorus are dispersed in the mixed solution of NMP and DMF, successively
Carry out ultrasound, mist projection granulating, heat treatment；The molar ratio of the additional amount of lithium source is in the additional amount and raw material of the red phosphorus
0.01:(1-1.1)；The temperature of the heat treatment is 450-550 DEG C, time 1.5-4.5h.
2. preparation method as described in claim 1, which is characterized in that in step (1), the lithium source is lithium carbonate, hydroxide
One of lithium, lithium acetate and lithium nitrate are a variety of；And/or the nickel source is nickel oxalate, nickel oxide, nickel nitrate and hydroxide
One of nickel is a variety of；And/or the manganese source be one of manganese acetate, manganese dioxide, mangano-manganic oxide and manganese nitrate or
It is a variety of；And/or the boron source is boric acid and/or diboron trioxide.
3. preparation method as described in claim 1, which is characterized in that in step (1), lithium source, nickel source, manganese source, the original of boron source
Sub- molar ratio Li:Ni:Mn:B=1.005:0.5:1.5:(0.005-0.02)；
And/or in step (1), the water is deionized water, and additional amount is that the solid content of solution is adjusted to 15%-
Amount needed for 45%, the percentage are mass percent；
And/or in step (1), described be uniformly mixed is realized by sanding operation.
4. preparation method as claimed in claim 3, which is characterized in that in step (1), the additional amount of the water is by solution
Solid content be adjusted to 20% needed for amount, the percentage be mass percent；
And/or in step (1), the equipment of the sand milling is sand mill；The time of the sand milling is 0.5-5h.
5. preparation method as claimed in claim 4, which is characterized in that the time of the sand milling is 1h.
6. preparation method as described in claim 1, which is characterized in that in step (3), the pre-burning carries out in Muffle furnace；
The temperature of the pre-burning is 350-550 DEG C, time 4-10h.
7. preparation method as described in claim 1, which is characterized in that in step (4), the high-temperature calcination in tube furnace into
Row；The temperature of the high-temperature calcination is 750-1000 DEG C, time 10-24h.
8. preparation method as described in claim 1, which is characterized in that in step (5), in the mixed solution of the NMP and DMF
The volume ratio of NMP and DMF is 2:1；And/or the mass ratio of the mixed solution and electrode material is 4:1；
And/or in step (5), the time of the ultrasound is 0.5-5h；
And/or in step (5), the temperature of the heat treatment is 500 DEG C, time 2h.
9. a kind of composite positive pole, which is characterized in that it is as the preparation method preparation as described in claim 1-8 any one
It obtains.
10. a kind of application of composite positive pole as claimed in claim 9 in lithium ion battery.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114094095A (en) * | 2021-11-09 | 2022-02-25 | 远景动力技术(江苏)有限公司 | Spinel type positive electrode material, preparation method thereof and lithium ion battery positive electrode plate |
| CN115799487A (en) * | 2023-02-08 | 2023-03-14 | 国联汽车动力电池研究院有限责任公司 | Boron-phosphorus co-doped modified lithium-rich manganese-based positive electrode material, and preparation method and application thereof |
| EP4048639A4 (en) * | 2019-10-24 | 2023-11-29 | Camx Power LLC | Precursor materials for li-ion battery cathode synthesis |
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| Publication number | Priority date | Publication date | Assignee | Title |
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